Thiazole derivatives

ABSTRACT

An organic compound of the general formula ##STR1## where R 1  and R 2  are cyano, formyl, substituted or unsubstituted alkanoyl or aroyl, a carboxylic acid ester group, substituted or unsubstituted carbamoyl or sulfamoyl, alkylsulfonyl, arylsulfonyl or alkylsulfinyl, or 
     R 1  and R 2  together may be a cyclic radical, 
     R 2  may also be alkyl, aryl or hetaryl, 
     R 3  is hydrogen, substituted or unsubstituted alkyl, aryl or hetaryl, 
     X is CH, CR 5  or N, 
     R 4  is a radical of the formula ##STR2## R 5  to R 10  are substituents conventionally present in dyes. The compounds may be used as dyes for synthetic and natural fibers and give very fast dyeings.

The present invention relates to a compound of the general formula I##STR3## where R¹ and R² are cyano, formyl, substituted or unsubstitutedalkanoyl or aroyl, a carboxylic acid ester group, substituted orunsubstituted carbamoyl or sulfamoyl, alkylsulfonyl, arylsulfonyl oralkylsulfinyl,

R¹ and R² together may be a cyclic radical,

R² may also be alkyl, aryl or hetaryl,

R³ is hydrogen, substituted or unsubstituted alkyl, aryl or hetaryl,

X is CH, CR⁵ or N, and

R⁴ is a radical of the formula ##STR4## where R⁵ to R¹⁰ are substituentsconventionally present in dyes.

More particularly, the invention relates to a compound where

R⁵ is alkyl of 1 to 4 carbon atoms, alkoxycarbonyl (where alkoxy is of 1to 4 carbon atoms), cyano or substituted or unsubstituted phenyl,

R⁶ is hydrogen, chlorine, bromine, methyl, hydroxyl, alkoxy of 1 to 4carbon atoms, alkanoylamino of 1 to 4 carbon atoms or benzoylamino,

R⁷ and R⁸ independently of one another are hydrogen or alkyl of 1 to 5carbon atoms which is unsubstituted or substituted by hydroxyl,chlorine, cyano, alkoxy of 1 to 4 carbon atoms, alkanoyloxy of 1 to 4carbon atoms or alkoxycarbonyl (where alkoxy is of 1 to 4 carbon atoms),or are allyl, cyclohexyl, benzyl, phenylethyl or phenyl,

R⁹ is hydrogen, chlorine, bromine or alkyl of 1 to 4 carbon atoms and

R¹⁰ is methyl or phenyl.

Specific examples of radicals R¹, in addition to those alreadymentioned, are: COCH₃, COC₂ H₅, COC₃ H₇, COCH₂ Cl, COCHCl₂, COC₆ H₅,COC₆ H₄ Cl, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₅, COO(CH₂)₃OCH₃, COO(CH₂)₃ OC₂ H₅, CONHCH₃, CONHC₂ H₅, CONHC₃ H₇, CONHC₄ H₉,CON(CH₃)₂, CON(C₂ H₅)₂, CONH₂, CONHC₆ H₅, ##STR5## and ##STR6## and thecorresponding sulfamoyl radicals, CH₃ SO₂, C₂ H₅ SO₂, C₄ H₉ SO₂ or CH₃SO.

R² may be identical with R¹ ; specific examples of its alternativemeanings are: CH₃, C₂ H₅, C₆ H₅, C₆ H₄ Cl, CH₃ OOC--C₆ H₄, O₂ N--C₆ H₄,NC--C₆ H₄, CH₃ COC₆ H₄, ##STR7##

R¹ and R² together may also form a cyclic radical, for example: ##STR8##

Examples of radicals R³ are: CH₃, C₂ H₅, C₄ H₉, C₆ H₅, alkyl--OC₆ H₄(where alkyl is of 1 to 4 carbon atoms), Cl--C₆ H₄, BrC₆ H₄,alkyl--S--C₆ H₄ (where alkyl is of 1 to 4 carbon atoms), H₅ C₆ S--C₆ H₄or CH₂ --COO-alkyl (where alkyl is of 1 to 4 carbon atoms).

Examples of radicals R⁵ are cyano and CH₃, C₂ H₅, C₃ H₇, C₄ H₉, COOCH₃,COOC₂ H₅, COOC₄ H₉, C₆ H₅, C₆ H₄ Cl, C₆ H₄ Br, C₆ H₄ CH₃, C₆ H₄ OCH₃, C₆H₄ OC₂ H₅, C₆ H₄ SCH₃, C₆ H₄ N(CH₃)₂ and C₆ H₄ N(C₂ H₅)₂.

Specific examples of radicals R⁴ are radicals derived from aniline, ofthe formula ##STR9## where R⁶ is Cl, CH₃, OCH₃, OC₂ H₅, OC₃ H₇, NHCOCH₃,NHCOC₂ H₅ or NHCOC₃ H₇ and

R⁷ and R⁸ are CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₂ H₄ CN, C₂ H₄ COO-alkyl (wherealkyl is of 1 to 4 carbon atoms), C₂ H₄ OH, C₂ H₄ O-alkyl (where alkylis of 1 to 4 carbon atoms) or C₂ H₄ OCONH-alkyl (where alkyl is of 1 to4 carbon atoms).

The compound of the formula I may be prepared by condensing a thiazoleof the formula IIa or IIb ##STR10## with a compound of the formula III

    R.sup.4 --X═O                                          III

where

R¹, R², R³, R⁴ and X have the above meanings.

The condensation may be effected by heating the compounds I and II in asolvent--virtually all solvents being suitable--at from 30° to 160° C.,preferably from 60° to 100° C. Examples of suitable solvents aremethanol, ethanol, propanol, butanol, methylglycol, dioxane, acetone,acetonitrile, DMF, NMP, water, toluene, xylene, chlorobenzene andnitrobenzene.

The condensation is accelerated by adding acid or basic catalysts. Thewater formed during the reaction can be removed azeotropically from thereaction mixture.

Examples of suitable catalysts are mineral acids, carboxylic acids, eg.formic acid, acetic acid and trichloroacetic acid, phosphorusoxychloride, phosphorus pentachloride, phosphorus trichloride or thionylchloride.

Examples of basic catalysts are ammonium acetate and amines, eg.piperidine, pyrrolidine, pyridine, triethylamine and triethanolamine.

Details of the method of preparation may be found in the Examples, whereparts and percentages are by weight, unless stated otherwise.

The majority of the compounds of the formula IIa and b are new. They maybe prepared, for example, by a method similar to that described inGerman Laid-Open Application DOS No. 1,913,472. Some compounds of theformula IIa and b are described in J. prakt, Chem., 316 (1974), 684.

Compounds of particular industrial importance are those of the formulaIa ##STR11## where B¹ and B² are cyano, alkoxycarbonyl (where alkoxy isof 1 to 4 carbon atoms), alkanoyl of 1 to 4 carbon atoms or substitutedcarbamoyl,

B³ is phenyl which is unsubstituted or substituted by chlorine, bromine,methoxy, ethoxy, methyl or alkylmercapto of 1 to 4 carbon atoms and

B⁴ is a radical of the formula ##STR12## where R⁶ to R⁹ have the abovemeanings; preferred meanings are as follows:

R⁶ : hydrogen, NHCOCH₃, CH₃, OCH₃, HNCOC₂ H₅ and Cl.

R⁷ and R⁸ : hydrogen, CH₃, C₂ H₅, CH₂ --CH═CH₂, C₂ H₄ CN, C₂ H₄COO-alkyl (where alkyl is of 1 to 4 carbon atoms), C₆ H₅, CH₂ C₆ H₅ andC₂ H₄ OCOCH₃.

R⁹ : C₆ H₅ and CH₃.

The dyes of the formula I are violet to yellowish green and areparticularly suitable for dyeing polyester fibers. They give brilliantvery fast dyeings; the lightfastness, wetfastness and fastness to heattreatments are to be singled out particularly.

The particular industrial importance of the novel dyes resides in thefact that they may be used to produce green hues on polyester withouthaving to resort to the use of dye mixtures.

The dyes are also suitable for printing polyester/cotton union fabrics,for example by the process described in German Pat. No. 1,811,796.

EXAMPLE 1

21 parts of methyl 4-phenyl-thiazol-2-yl-cyanoacetate, 15 parts ofp-nitroso-dimethylaniline hydrochloride, 10 parts of glacial acetic acidand 5 parts of ammonium acetate in 300 parts of toluene are refluxed,the water formed in the reaction being removed. After 4 hours themixture is cooled and the dye is filtered off.

Yield: 35 parts. Melting point: 246° C. λ_(max) in DMF: 655 nm.

The following dyes were prepared by a method similar to that describedin Example 1:

    __________________________________________________________________________                                            Hue on                                Ex- Thiazole           Carbonal or      poly-                                 ample                                                                             component          nitroso compound ester                                 __________________________________________________________________________         ##STR13##                                                                                        ##STR14##       blue                                  3   "                                                                                                 ##STR15##       reddish blue                          4   "                                                                                                 ##STR16##       greenish blue                         5   "                                                                                                 ##STR17##       greenish blue                         6   "                                                                                                 ##STR18##       greenish blue                         7   "                                                                                                 ##STR19##       greenish  blue                        8   "                                                                                                 ##STR20##       greenish- blue                        9   "                                                                                                 ##STR21##       green                                 10  "                                                                                                 ##STR22##        "                                    11                                                                                 ##STR23##                                                                                        ##STR24##       blue                                  12  "                                                                                                 ##STR25##        "                                    13  "                                                                                                 ##STR26##        "                                    14  "                                                                                                 ##STR27##       violet                                15  "                                                                                                 ##STR28##       green                                 16  "                                                                                                 ##STR29##       yellowish green                       17  "                                                                                                 ##STR30##       yellowish green                       18  "                                                                                                 ##STR31##       yellow- ish green                     19  "                                                                                                 ##STR32##       bluish green                          20  "                                                                                                 ##STR33##       bluish green                          21  "                                                                                                 ##STR34##       green                                 22  "                                                                                                 ##STR35##        "                                    23  "                                                                                                 ##STR36##       green                                 24                                                                                 ##STR37##                                                                                        ##STR38##       yellow- ish green                     25                                                                                 ##STR39##         "                yellow- ish green                     26                                                                                 ##STR40##         "                yellow- ish green                     27                                                                                 ##STR41##         "                yellow- ish green                     28                                                                                 ##STR42##         "                violet red                            29                                                                                 ##STR43##                                                                                        ##STR44##       green                                 __________________________________________________________________________

EXAMPLE 30

2 ml of phosphorous oxychloride are added to 6.4 parts of methyl4-phenyl-thiazol-2-yl-cyanoacetate and 6.7 parts of Michler's ketone in75 ml of chlorobenzene, and the mixture is heated at 60° C. After 3hours it is poured onto ice and the organic phase is separated off,dried and concentrated.

Yield: 9 parts. Melting point: 98° C.

EXAMPLE 31

11.6 parts of 4-phenyl-thiazol-2-yl-malodinitrile, 16 parts of3-methoxy-4-nitroso-diphenylamine and 1 drop of piperidine are refluxedin alcohol for 1 hour. After cooling, the dye is filtered off.

Yield: 18 parts of needles having a metallic sheen.

EXAMPLE 32

15 parts of 4-phenyl-thiazol-2-yl-cyanoacet-n-butylamide and 13 parts of4-nitroso-cyanoethyl-ethylaniline hydrochloride in 100 parts of alcoholare boiled for 2 hours, after which the mixture is cooled and the dye isfiltered off.

Yield: 13 parts of deep blue needles.

The compounds of Examples 33-81 were prepared by methods similar to thatdescribed in Example 32.

    __________________________________________________________________________                                                  Hue on                          Ex-                            Carbonyl or    poly-                           ample                                                                             Thiazole component         nitroso compound                                                                             ester                           __________________________________________________________________________    33                                                                                 ##STR45##                                                                                                ##STR46##     blue                            34  "                                                                                                         ##STR47##     green                           35                                                                                 ##STR48##                                                                                                ##STR49##     bluish green                    36  "                                                                                                         ##STR50##     green                           37                                                                                 ##STR51##                                                                                                ##STR52##     bluish green                    38                                                                                 ##STR53##                                                                                                ##STR54##     green                           39  "                                                                                                         ##STR55##     bluish green                    40                                                                                 ##STR56##                                                                                                ##STR57##     blue                            41  "                                                                                                         ##STR58##     bluish green                    42  "                                                                                                         ##STR59##     green                           43                                                                                 ##STR60##                                                                                                ##STR61##     green                           44                                                                                 ##STR62##                                                                                                ##STR63##     violet                          45  "                                                                                                         ##STR64##     violet                          46                                                                                 ##STR65##                                                                                                ##STR66##     violet red                      47                                                                                 ##STR67##                                                                                                ##STR68##     reddish violet                  48                                                                                 ##STR69##                                                                                                ##STR70##     reddish violet                  49.sup.1                                                                           ##STR71##                                                                                                ##STR72##     bluish green                    50.sup.1                                                                          "                                                                                                         ##STR73##     bluish green                    51                                                                                 ##STR74##                                                                                                ##STR75##     green                           52                                                                                 ##STR76##                 "              "                               53                                                                                 ##STR77##                 "              "                               54                                                                                 ##STR78##                 "              "                               55                                                                                 ##STR79##                 "              "                               56                                                                                 ##STR80##                 "              "                               57                                                                                 ##STR81##                 "              "                               58                                                                                 ##STR82##                 "              "                               59                                                                                 ##STR83##                 "              "                               60                                                                                 ##STR84##                 "              "                               61                                                                                 ##STR85##                                " -62                                                                          "#"TR86##                      63                                                                                 ##STR87##                 "              "                               64                                                                                 ##STR88##                 "              "                               65                                                                                 ##STR89##                 "              "                               66                                                                                 ##STR90##                 "              "                               67                                                                                 ##STR91##                 "              "                               69                                                                                 ##STR92##                 "              "                               69                                                                                 ##STR93##                 "              "                               70                                                                                 ##STR94##                 "              "                               71                                                                                 ##STR95##                 "              "                               72                                                                                 ##STR96##                                                                                                ##STR97##     olive                           73                                                                                 ##STR98##                 "              olive                           74                                                                                 ##STR99##                 "              olive                           75                                                                                 ##STR100##                "              green                           76                                                                                 ##STR101##                                                                                               ##STR102##    green                           77                                                                                 ##STR103##                                                                                               ##STR104##    green                           78                                                                                 ##STR105##                "              green                           79                                                                                 ##STR106##                                                                                               ##STR107##    green                           80                                                                                 ##STR108##                "              green                           81                                                                                 ##STR109##                                                                                               ##STR110##    green                           __________________________________________________________________________     .sup.1 in boiling DMF                                                    

We claim:
 1. A compound of the formula ##STR111## where B¹ and B² arecyano, alkanoyl of 1 to 4 carbon atoms, benzoyl which is unsubstitutedor substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4carbon atoms, COOB⁵ or ##STR112## B³ is phenyl which is unsubstituted oris monosubstituted or polysubstituted by chlorine, bromine, alkoxy of 1to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, phenoxy, alkylmercaptoof 1 to 4 carbon atoms, phenylmercapto, β-cyanoethoxy, β-C₁ - to C₄-alkoxycarbonyl-ethoxy or β-cyanoethylthio, or is thienyl,B⁴ is aradical of the formula ##STR113## B⁵ is alkyl of 1 to 8 carbon atoms, oris alkyl of 2 or 3 carbon atoms substituted by alkoxy of 1 to 8 carbonatoms, chlorine, bromine, phenyl or C₁ to C₄ -alkoxyethoxy, B⁶ and B⁷independently of one another are hydrogen, alkyl of 1 to 8 carbon atomsor alkyl of 2 or 3 carbon atoms which is substituted by alkoxy of 1 to 4carbon atoms, C₁ - to C₄ -alkoxyethoxy, phenoxyethoxy, cyano, C₁ to C₄-alkoxycarbonyl, alkanoyloxy of 1 to 4 carbon atoms or phenyl, or arecyclohexyl or phenyl, B⁶ and B⁷ together with the nitrogen may also bepyrrolidino, piperidino or morpholino, R⁶ is hydrogen, chlorine,bromine, methyl, hydroxyl, alkoxy of 1 to 4 carbon atoms, alkanoylaminoof 1 to 4 carbon atoms or benzoylamino, R⁷ and R⁸ independently of oneanother are hydrogen or alkyl of 1 to 5 carbon atoms which isunsubstituted or substituted by hydroxyl, chlorine, cyano, alkoxy of 1to 4 carbon atoms, alkanoyloxy of 1 to 4 carbon atoms or C₁ - to C₄-alkoxycarbonyl, or are allyl, cyclohexyl, benzyl, phenylethyl orphenyl.
 2. The compound as claimed in claim 1, whereB¹ and B² are cyano,COOB⁵ or ##STR114## B³ is phenyl which is unsubstituted or ismono-substituted or polysubstituted by chlorine, alkoxy of 1 to 5 carbonatoms, alkyl of 1 to 5 carbon atoms or β-cyanoethoxy, B⁴ is a radical ofthe formula ##STR115## B⁵, B⁶, B⁷, R⁶, R⁷ and R⁸ have the abovemeanings.
 3. The compound as claimed in claim 2, whereB⁵ is alkyl of 1to 4 carbon atoms, or is alkyl of 2 or 3 carbon atoms substituted byalkoxy of 1 to 4 carbon atoms, B⁶ and B⁷ independently of one anotherare hydrogen, alkyl of 1 to 4 carbon atoms or alkyl of 2 or 3 carbonatoms which is substituted by alkoxy of 1 to 4 carbon atoms, C₁ - to C₄-alkoxyethoxy or phenoxyethoxy, or are phenyl,and the remainingsubstituents have the above meanings.
 4. The compound as claimed inclaim 2, whereR⁶ is hydrogen, chlorine, methyl, methoxy or acetylamino,R⁷ and R⁸ independently of one another are alkyl of 1 to 5 carbon atomsor alkyl of 2 or 3 carbon atoms which is substituted by hydroxyl, cyano,alkoxy of 1 to 4 carbon atoms, alkanoyloxy of 1 to 4 carbon atoms orC₁ - to C₄ -alkoxycarbonyl, or are allyl or phenylethyl and theremaining substituents have the above meanings.
 5. The compound asclaimed in claim 2 of the formula ##STR116## where B⁸ and B⁹independently of one another are alkyl of 1 to 4 carbon atoms,B¹⁰ ishydrogen, alkyl of 1 to 5 carbon atoms or chlorine and B⁵ has the abovemeaning.